Condensation products of melamineb



Patented Jan. 14, 1947 'CONDENSATION PRODUCTS F MELAMINES ANDSUBSTITUTED MELADIINES WITH ALKYLENE OXIDES Walter P. Ericka, Buffalo,N. Y., minor to American Cyanamid Company, New York, N. Y., acorporation of Maine No Drawing. Original application January 1'1,

1941, Serial No. 374,834. Divided and this application December 24,1943, Serial No. 515,609

7 Claims.

This invention relates to the preparation of new and useful reactionproducts of triazines and substituted triazlnes with alkylene oxides.

More particularly, it embraces the preparation of reaction products byreacting triazines such as melamine and substitution and polymerizationproducts thereof with alkylene oxides such as ethylene oxide, glycidolor compounds capable of yielding an alkylene oxide-containing substanceduring the condensation reaction. This case is a division of myco-pending application, Ser. No. 374,834, filed Jan. 17, 1941, nowPatent No. 2,381,- 121.

It is an object of this invention to prepare these compounds cheaply andefflciently. A still further object is to prepare surface activematerials which find use a textile and leather assistants and in thepaper, lacquer, resin, cosmetic and similar industries as highlyeffective wetting, emulsifying and detergent agents. The products ofthis invention are especially useful for softening purposes as well asanti-crease and wrinkle prevention in cloth, leather, Fabrikoid andsimilar materials and are particularly valuable when used as alkali andacid resistant wetting, detergent and emulsifying agents, as well as forthe resolution of emulsions such as petroleum emulsions. They also finduse as mercerizing assistants. Further and more important uses aresuggested in the following description.

With these objects in view and such others as may hereinafter appear,the invention consists in the novel products and processes describedbelow and more particularly defined in the claims.

The necessary reactants are mixed together with a diluent or asalternatively described with a portion of a recycled liquid reactionproduct. The product is then obtained by evaporation of the diluent.

The compounds of this invention are prepared in general by reacting atriazine, substituted or unsubstituted with a compound containing anethylene oxide ring. If desired the reaction is accelerated by using atemperature of 150 to 200 C. and a suitable organic or inorganic base,preferably an alkali-metal or alkaline earth metal hydroxide, such assodium hydroxide, potassium hydroxide, and calcium hydroxide, orpyridine, and the like. Usually the reaction is exothermic and hencemust be controlled as by the use of an efficient cooling device. Threaction product is then filtered off, washed and dried on a steam bath.If desired, complete condensation of the reactants is not effected.Instead, the reaction is temporarily arrested and completed only afterExample I 6.3 g. of melamine (0.05 mol.) and 11.1 g. of glycidol (0.15mol.) were heated slowly with stirring to l30 C. whereupon the externalheating was discontinued. The stirring was continued and the temperaturerose slowly to 140 C. At

this temperature a sudden reaction took place and even after the beakerwas placed in ice water, the temperature of the reaction medium rose to220 C. The product was a non-transparent soft resin, soluble in hotwater, from which a precipitate (probably unreacted melamine) wasobtained on cooling. Upon heating the resinous product to 250 C. itassumed an amber color, became viscous and was soluble in both hot andcold water.

Example II 1.26 g. of melamine (0.01 mol.) and 7.4 g. of glycidol (0.1mol.) were heated slowly with constant stirring to 140 C. Even after thereaction mixture and its container were placed into cold water, thereaction temperature rose continuously to 220 C. The product was anamber colored, transparent, very viscous resin which was readily solublein hot water.

Example III octadecoxy propylamine hydrochloride was prepared byreacting octadecoxy primary amine with an equimolecular quantity ofhydrochloric acid in ethyl alcohol and subsequently filtering off theproduct obtained.

18.2 g. of octadecoxypropylamine hydrochloride (0.05 mol.) and 3.15 g.of melamine (0.025 mol.) were heated at 200 to 210 C. for 3 hours. Thebrown colored product obtained was allowed to cool, and then ground anddigested in warm water containing an excess of ammonia. The resultantslurry was cooled in an ice bath, filtered, the filter cake was washedwith water and digested in hot alcohol containing charcoal. The alcoholextract was filtered and the filtrate was evaporated on a hot plate andsubsequently on a steam bath to yield a tan colored wax, solidifying atabout C. and weighing about 13 g.

One moi. equivalent of this bis-octadecoxy- In addition to ethyleneoxide and glycidol, varipropyl melamine was reacted in a container withous other ethylene oxide ring compounds may be twenty mo]. equivalentsof glycidol by heating the used, namely propylene oxide, isobutyleneoxide.

reactant to 250 C. The product obtained was tetramethylene oxide,n-hexyi-ethylene oxide and soluble in cold water and common organicsolepichlorhydrin as well as compounds which are vents and gave clearfoaming solutions. The recapable of forming an ethylene oxide ring underaction probably takes place according to the forthe conditions of thereaction as, for example, mule: ethylene chlorhydrin, chloroglycerol andthe like.

llis-octadccoxypropyl melamine aiycidol r ummocum, c

CH one]! on N/ \N x i 11111031150 G b-n81 II I lIN-C U-NHCaUsO CuHa':

nocrncncmnociht zncih- N N i H l The duct was soluble and stable instrong Various alkylene oxides or alkylene oxide containalkalinesolutions and exhibited strong wetting me compounds may be used.However, if the properties. It could be used advantageously as acompound chosen for the reaction with a trlazine mercerizing assistant.has a low boiling point, i. e. ethylene oxide, prop- Example IV yleneoxide, and the like, it'is advantageous to carry out the reaction in aclosed system and In another experiment. 8. of bis-octadecunder elevatedpressure in order to raise the tem- YP DY melamine (0111 11101) and -88- Of perature of the reaction to a point at which the glycidol (0.2mol.) were heated to 170 C. when reaction proceedsat a sufiicientlyrapid rate to an exothermic reaction occurred, the heatin make theprocess commercially feasible. being discontinued, sending thetemperature to These reaction products of compounds contain- 220- C. Thereaction mixture was cooled to 190 ing an ethylene oxide ring and atriazine or a C. and then heated to 190 to 200 C. for 15 min substitutedtriazine are of particular utility in the utes to yield a brown wax,easily soluble in hot formation of surface-active agents of thecationwater and readily dispersible in cold water. The active type. Forthis reason they are well suited P ct S ed excellent Softening P p t forwetting and softening wool, cotton, cellulose when applied to cellulosicfabrics, yarn or threads. t t cellulose t t viscose and similar ExampleV terials. They are also useful in the emulsification of mineral oils,glycerides, fats, oils and the like.

6.3 g. of melamine (0.05 mol.) and a plurality They find application inthe formulation of printf Portions 0f Elyeidol (015 Per ing inks, dyepastes, dye baths, leather preparation) up to about two Portions 4 tionsand flotation agents. By their use it is posglyeifiol were reacted byheating to wlth sible to secure fullness, resistance to unraveling, Atthis temperature a repld nee and increased wet strength in rayons andother temperature Occurred and the heating was fabrics. They reduce thetendency of treated continued, the beaker and its contents being imclothmaterials to wrinkle or creasa mersed 111 an ice bath- The temperatureof the These products, particularly those having waxy reaction leeehedend on cooling e white or paste-like properties are useful assistants inhard resin formed. The product was soluble in the textile, leather,paper rubber lacquer and hot water, precipitating out upon cooling. Thissimilar industries. In many of the examples, parmelamine-glycidolcondensation product was then ti lafl when polyamines are incorporated,or heated-together an additional 01 8.1 when temperatures are notcarefully regulated Portlon of glycldol' At an exothermic mixturesresult containing several different subreaetion book Place and thetemperature to stances. When used as textile assistants or in on eeohhga Very Viscous, Opalesceht leather and similar processing industries itis not resin was obtaineq- This h was f h necessary to isolate thedesired products; instead, ble in hot water without forming aprecipitate on the mixtures can be used directly COOhng- The bottom ofthe beaker, however still The products described herein may be furtherheld 8, small quantity Of unreacted melamine. reacted with an amineeither primar or sec- This reaction mass was further reacted with aondary, or with a fatty acid to yield highly del 8- portion. of s d Thereaction sirable and useful surface-active compounds. mixture wasstirred and heated to 90 C. at which In ti n t the triazines abovementioned temperature the application of external heat was variousothers may be reacted t th alkylene discontinued and by continuing thestirring 0f xides Among such compounds may be specifithe mixture thetempemhu'e was maintained at cally cited cyanuric chloride, itssubstitution prodabout 15 minutes because of the ucts such as cyanuricacid for polymerization thermle reaction which set when the products ofthese triazines such as melam, melem, n ra re began to drop. a smallquantity (about melon, hydromelonic acid, and the like. Further 5 cc.) oWater was added. the mixture was heated examples of substitutedmelamines include mono-, to 140 C. and then a owed t 6001- A P 3 (11-,and tri-laurylmelamine, mono-, di-, and tri- W. viscous resin wasobtained, re y Soluble octadecylmelamine, benzylmelamine, mono-, di-, inwater. and triphenyl melamine and their isomers, monoformyi melamine,and other monoacyl derivatives, diacetyl melamine, triamino-meiamine,hexachloro-triphenyl melamine and other cyanuric chloro-anilides,tri-p-diphenylene-diamino-melamine, tricarbamine melamine,2,4,6-tri-p-naphthyl melamine and the like.

It is to be understood that the examples are merely specific embodimentsand that the invention is not limited thereto, but is to be broadlyconstrued within the. scope of the appended claims.

I claim:

1. A condensation product of glycidol and bisoctadecoxypropyl melamine.

2. A condensation product of glycidol and an octadecoxypropyl melaminecontaining a replaceable hydrogen atom attached to a nitrogen atom.

3. The process for the preparation of condensation products whichcomprises reacting a member selected from the group consisting ofmelamine, a hydrocarbon substituted melamine containing from 1 to 3monovalent hydrocarbon substituents attached to amine nitrogen and anoctadecoxypropyl melamine, with a, compound containing an alkylene oxidering.

4. The process for the preparation or condensation products whichcomprises reacting a member selected from the group consisting ofmelamine, a hydrocarbon substituted melamine containing from 1 to 3monovalent hydrocarbon substituents attached to amine nitrogen and anoctadecoxypropyl melamine, with a compound containing'an ethylene oxidering.

5. The condensation product of a compound containing an alkylene oxidering and a member selected from the group consisting of melamine, ahydrocarbon substituted melamine containing from 1 to 3 monovalenthydrocarbon substituents attached to amine nitrogen and anoctadecoxypropyl melamine.

6. The condensation product of a compound containing an ethylene oxidering and a member selected from the group consisting of melamine, ahydrocarbon substituted melamine containing from 1 to 3 monovalenthydrocarbon substituents attached to amine nitrogen and anoctadecoxypropyl melamine.

7. The condensation product of glycidol and a member selected from thegroup consisting of melamine, a hydrocarbon substituted melaminecontaining from 1 to 3 monovalent hydrocarbon substituents attached toamine nitrogen and an octadecoxypropyl melamine.

WALTER P. ERICKS

